Ionomer laminates, composite articles, and processes for making the same

ABSTRACT

The present invention relates to new combinations of tie-layers and backing layers and/or substrates for making (1) new multilayer structures formed from one or more ionomers and one or more tie-layers, and optionally a backing layer to form laminates, (2) new composite articles made from these laminates in combination with optional substrate materials, and (3) new methods of making composite articles from these laminates by shaping and subsequently contacting them with a substrate material.

FIELD OF THE INVENTION

The present invention relates to new combinations of tie-layers andbacking layers and/or substrates for making (1) new multilayerstructures formed from one or more ionomers and one or more tie-layers,and optionally a backing layer to form laminates, (2) new compositearticles made from these laminates in combination with optionalsubstrate materials, and (3) new methods of making composite articlesfrom these laminates by shaping and subsequently contacting them with asubstrate material.

BACKGROUND OF THE INVENTION

Durable, glossy fascia associated with articles such as automobiles,luggage, appliances, and other durable articles made from plasticsincrease both the aesthetic appeal and the utility of these articles.These article attributes are provided, in part, through theincorporation of ionomer materials.

Ionomer materials are known in the art, and are useful in laminates tocoat various substrates to form composite articles. See, for example,U.S. Pat. Nos. 5,482,766, 4,148,972, 5,543,233, 4,800,130, 4,656,098,5,206,294, 4,335,175, U.S. Patent Application Publication No.2002/0055006 A1, DE 36 26 809 A, EP 0 721 856, JP 08269409, JP2000085062, JP 04052136, WO 01/78981, WO 02/078953 and WO 02/078954.Ionomer laminates are useful for their scratch and abrasion resistance,as well as toughness and aesthetic appeal. However, with a growingdemand for new applications for ionomer laminates and composite articlesproduced from ionomer laminates, there continues to be a need for newcombinations of materials to produce new laminates for the wide array ofapplications.

The invention fulfills this need by providing for new combinations oftie-layer and backing layer and/or substrate materials that may be usedin new ionomer laminates and new composite articles.

SUMMARY OF THE INVENTION

In an embodiment, the invention relates to a composite comprising anionomer layer, a tie-layer, and a substrate.

In an embodiment, the invention relates to a composite comprising anionomer layer, a tie-layer, and a substrate wherein the tie-layer isdisposed between the ionomer layer and the substrate.

In yet another embodiment, the invention relates to a composite articlecomprising:

-   -   a) an ionomer layer;    -   b) a tie-layer;    -   c) a backing layer; and    -   d) a substrate;    -   wherein the tie-layer and backing layer are disposed between the        ionomer layer and the substrate.

Additionally, the invention also provides for a method of forming acomposite article comprising:

-   -   (a) forming a laminate;    -   (b) forming the laminate into a shape, the laminate comprising        an ionomer layer contacted to a tie-layer; and    -   (c) securing a substrate to the tie-layer of the laminate to        form the composite article.

In another embodiment, the invention provides for a method of forming acomposite article comprising:

-   -   (a) coextruding at least two materials to form a laminate;    -   (b) thermoforming the laminate into a shape, the laminate        comprising an ionomer layer contacted to a tie-layer; and    -   (c) injection molding a substrate layer to the tie-layer of the        laminate to form the composite article.

The invention also provides for a composite article formed by the methodcomprising:

-   -   (a) forming a laminate comprising an ionomer layer and a        tie-layer;    -   (b) coextruding the ionomer layer and the tie-layer with a        backing layer;    -   (c) forming a shape from the laminate, resulting in a shaped        laminate; and    -   (d) securing a substrate material to the shaped laminate such        that the substrate material is secured to the backing layer.

In any of the previous embodiments, the ionomer layer may include afirst ionomer layer and a second ionomer layer.

In the previous embodiments, the first ionomer layer or the secondionomer layer may be pigmented, natural, or clear.

In any of the embodiments, a tie layer may comprise at least oneacid-containing polymer; and a backing layer and/or a substrate maycomprise at least one polyamide polymer; at least one polyamidecompound; at least one polyamide elastomer; or mixtures thereof.

In any of the embodiments, a tie layer may comprise at least oneamine-containing polymer; and a backing layer and/or a substrate maycomprise at least one nitrogen containing engineering thermoplasticpolymer; at least one polyamide polymer; at least one polyamidecompound; at least one polyamide elastomer; at least one polyurethanepolymer; or at least one polystyrene maleic anhydride; or mixturesthereof.

In any of the embodiments, a tie layer may comprise at least oneanhydride-containing polymer; and a backing layer and/or a substrate maycomprise at least one engineering thermoplastic polymer; at least onepolyamide polymer; at least one polyamide compound; at least onepolyamide elastomer; at least one polyester polymer; at least onepolyurethane polymer; at least one crosslinked polyester composition; orat least one ethylene vinyl alcohol copolymer; or mixtures thereof.

In any of the embodiments, a tie layer may comprise at least oneepoxy-containing polymer; and a backing layer and/or a substrate maycomprise at least one engineering thermoplastic polymer; at least onepolyamide polymer; at least one polyamide compound; at least onepolyamide elastomer; at least one polyester polymer; at least onepolyurethane polymer; polystyrene maleic anhydride; at least onecrosslinked polyester composition; or at least one ethylene vinylalcohol copolymer; or mixtures thereof.

In any of the embodiments, a tie layer may comprise at least one estercopolymer; and a backing layer and/or a substrate may comprise at leastone polyamide polymer; at least one polyamide compound; at least onepolyamide elastomer; at least one acrylic polymer; at least oneelastomer; at least one styrenic polymer; at least one copolymercontaining cyclic monomer(s); or at least one polyurethane polymer; ormixtures thereof;

In any of the previous embodiments, the tie layer may be selected fromany of the materials herein defined.

In any of the previous embodiments, the backing layer and/or substrate,alone or in combination with (blended or layered), may be selected fromany of the materials herein defined.

DETAILED DESCRIPTION OF THE INVENTION

Various specific embodiments of the invention will now be described,including exemplary embodiments and definitions that are adopted hereinfor purposes of understanding the claimed invention. However, forpurposes of determining infringement, the scope of the “invention” willrefer to the appended claims, including their equivalents, and elementsor limitations that are equivalent to those that are recited. Anyreference to the “invention” may refer to one or more, but notnecessarily all, of the inventions defined by the claims. References tospecific “embodiments” are intended to correspond to claims coveringthose embodiments, but not necessarily to claims that cover more thanthose embodiments.

As used herein, the term “Groups” or “Group” refers to the new numberingscheme for the Periodic Table Groups as in HAWLEY'S CONDENSED CHEMICALDICTIONARY 852 (13th ed. 1997).

As used herein, the term “layer” refers to each of the one or morematerials, the same or different, in an essentially planar form, thatare secured to one another by any appropriate means such as by aninherent tendency of the materials to adhere to one another, or byinducing the materials to adhere as by a heating, radiative, chemical,or some other appropriate process to form laminates.

As used herein, the term “laminate” refers to any number of the same ordifferent materials in layer form, each layer being secured to oneanother by any appropriate means such as by an inherent tendency of thematerials to adhere to one another, or by inducing the materials toadhere as by a heating, radiative, chemical, or some other appropriateprocess. Some non-limiting process examples of forming laminates are(co)extrusion, thermal lamination, or adhesive bonding, or somecombination thereof. The laminate may include an optional backing layer.

As used herein, the term “tie-layer” refers to a layer bonded to theionomer layer(s). In most embodiments that include a backing layer, thebacking layer is bonded to the ionomer layer(s) with the tie-layer. Insome embodiments that include a substrate, the substrate is bonded tothe ionomer layer(s) with the tie-layer. Each tie-layer may comprisemultiple layers.

As used herein, “backing layer” refers to a tie-layer that forms thesurface opposite from the ionomer surface of the multilayered laminate.In most embodiments, the backing layer requires a tie-layer of adifferent composition to bond it to the ionomer layer(s).

As used herein, “composite article” refers to an article formed from amultilayer laminate secured to a substrate.

As used herein, “substrate” refers to that part of the composite articlethat is behind the multilayered laminate, and typically provides thelargest proportion of the mass of the composite article. It thereforegoverns the range of many of the physical properties of the compositearticle such as stiffness, tensile strength, impact strength, etc.Surface properties of the composite article, such as gloss, scratchresistance, abrasion resistance, color, appearance, “flop”, are usuallyunaffected by the substrate.

As is well known in the art, the demarcation between “film” and “sheet”is nominally 250 μm. However, as used herein the term “sheet” can referto single layered or multilayered structures with thicknesses that aregreater than, equal to or less than 250 μm.

As used herein, the term “polymerization” includes homopolymerization,copolymerization, terpolymerization, and interpolymerization.

As used herein, the term “polymer” may be used to refer to homopolymers,copolymers, interpolymers, terpolymers, etc. Likewise, a copolymer mayrefer to a polymer comprising at least two monomers, optionally withother monomers. Polymer may also refer to one or more polymersregardless of the method, time, and apparatuses used to combine thepolymers. Additionally, polymer may be used to refer to polymericcompositions.

When a polymer is referred to as comprising a monomer, the monomer ispresent in the polymer in the polymerized form of the monomer or in thederivative form the monomer. However, for ease of reference the phrasecomprising the (respective) monomer or the like is used as shorthand.

As used herein, the term “elastomer,” “rubber,” or “elastomericcomposition,” refers to any polymer or composition of polymersconsistent with the ASTM D1566 definition. The terms may be usedinterchangeably with the term “rubber(s)”, as used herein.

In an embodiment, the composite article provides for a multilayeredsheet secured to a substrate. The multilayered sheet provides for anionomer layer (surface layer), pigmented or natural color, and atie-layer, pigmented or natural color. The multilayered sheet is securedto a substrate.

In another embodiment, the composite article provides for a multilayeredsheet including a backing layer. The multilayered sheet provides for anionomer layer (surface layer), pigmented or natural color, a tie-layer,pigmented or natural color, and a backing layer.

In another embodiment, the composite article provides for a multilayeredsheet secured to a substrate. The multilayered sheet provides for a setof ionomer layers comprising a surface layer of clear ionomer and asub-surface layer of pigmented or clear ionomer, and a pigmented ornatural color tie-layer. The multilayered sheet is secured to asubstrate.

The composite article also provides for a multilayered sheet, includinga backing layer, secured to a substrate. The multilayered sheet providesfor a set of ionomer layers comprising a surface layer of clear ionomerand a sub-surface layer of pigmented or clear ionomer, a pigmented ornatural color tie-layer, and a pigmented or natural color backing layer.

In yet another embodiment, the composite article provides for amultilayered sheet including a backing layer secured to a substrate. Themultilayered sheet provides for an ionomer layer (surface layer),pigmented or natural color, a tie-layer, pigmented or natural color, anda pigmented or natural color backing layer. The multilayered sheet issecured to a substrate.

In an embodiment, the composite article provides for a multilayeredsheet including a backing layer secured to a substrate. The multilayeredsheet provides for a set of ionomer layers comprising a surface layer ofclear ionomer and a sub-surface layer of pigmented or clear ionomer, apigmented or natural color tie-layer, and a pigmented or natural colorbacking layer. The multilayered sheet is secured to a substrate.

In another embodiment, the composite article provides for a multilayeredsheet secured to a substrate. The multilayered sheet provides for a setof ionomer layers comprising a surface layer of clear ionomer and asub-surface layer of pigmented or clear ionomer, and a pigmented ornatural color tie-layer. The multilayered sheet is secured to asubstrate.

Ionomer

Ionomers useful in the present invention are ionic compounds which arecopolymers of C₂ to C₄ α-olefin derived units (ethylene is hereinincluded as an “α-olefin”), and C₃ to C₆ α,β-ethylenically unsaturatedcarboxylic acids, and which contain one or more kinds of metallic ororganic cations associated with at least 5% of the acidic pendant groupsof the polymer. Typical ionomers and methods of production are disclosedin, for example, U.S. Pat. Nos. 3,264,272, 4,911,451, 5,210,138, and5,929,174; and WO 98/52981, 95/11929, 96/23009, 97/11995, and 97/02317,and described in COMPREHENSIVE POLYMER SCIENCE 755-772 (Colin Booth &Colin Price, ed. Pergamon Press 1989), in particular relating toethylene-based materials.

The metal ion or ions suitable for forming the ionic copolymers of thepresent invention comprise mono, di or tri-valent metal ions in theGroups 1 through 13 of the Periodic Table of Elements. Embodimentsinclude the following metal ions: Na⁺, K⁺, Li⁺, Cs⁺, Ag⁺, Hg⁺, Cu⁺,Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Cu²⁺, Cd²⁺, Hg²⁺, Pb²⁺, Fe²⁺, Co²⁺, Ni²⁺,Zn²⁺, Al²⁺ Sc³⁺, Fe³⁺, Al³⁺ and Yt³⁺. In the various ions mentionedabove, Mg²⁺, Na⁺ and Zn²⁺ are metals used in desirable embodiments.Reaction of the carboxylic acid groups of the ionomer and a metal ionderived from a desirable metal compound (metal oxide, metal chloride,etc.) is referred to as “neutralization”.

The ionomers useful in the present invention, either alone or as a blendof two or more ionomers, generally include more than 60 wt % α-olefinderived units in one embodiment by weight of the ionomer, and more than70 wt % α-olefin derived units in another embodiment, and more than 80wt % α-olefin derived units in one embodiment, and more than 85 wt %α-olefin derived units in yet another embodiment, and less than 95 wt %α-olefin derived units in another embodiment, and less than 85 wt %α-olefin derived units in another embodiment, and less than 75 wt %α-olefin derived units in yet another embodiment, and from 60 to 95 wt %α-olefin derived units in another embodiment, wherein a desirable rangeof α-olefin derived units that make up the ionomer is any combination ofany upper limit with any lower limit described herein; and from 5 to 25wt % of α,β-ethylenically unsaturated carboxylic acid derived units inone embodiment, and from 1 to 15 wt % of α,β-ethylenically unsaturatedcarboxylic acid derived units in another embodiment, and from 8 to 20 wt% of α,β-ethylenically unsaturated carboxylic acid derived units inanother embodiment, wherein a desirable embodiment of a useful ionomermay comprise any upper wt % limit and any lower wt % limit of anyα,β-ethylenically unsaturated carboxylic acid derived units describedherein.

The polymer may be neutralized to form the ionomer to any degree between10% to 100% based on the total amount of neutralizable carboxylategroups in one embodiment, and from 20% to 80% in another embodiment, andfrom 40% to 75% in yet another embodiment, and from 5% to 70% in yetanother embodiment, provided the necessary scratch and mar resistance ismaintained. A desirable level of neutralization may include any upperneutralization % limit and any lower neutralization % limit describedherein.

One embodiment of an ionomer can be described as in the followingstructure (1):

wherein X¹ and X² can be the same or different and are hydrogen or a C₁to C₆ alkyl, and M^(n+) is a metal ion or NH₄ ⁺. Of course, it isunderstood that when n is >1, such as with a divalent metal ion such asZn²⁺, that charge neutrality for the ionomer is achieved by reactionwith a total of n acid groups from either the same polymer chain, or anadjacent polymer chain. The structure (1) is not intended to beconstrued that the ionomer is a block copolymer or limited to being ablock copolymer. The values of i, j, and k are determined by thefollowing relationships (2) and (3): $\begin{matrix}{\frac{j + k}{i + j + k} = Q} & (2) \\{\frac{k}{j + k} = P} & (3)\end{matrix}$wherein Q is from 10 to 40% of the polymer units derived from the acidicmonomer(s) relative to the total weight of the ionomer in oneembodiment, and from 15 to 20% of polymer units derived from the acidicmonomer(s) in another embodiment, and P is from 10 to 80% of the acidicgroups neutralized with the metallic ions in one embodiment, and from 20to 70% of the acidic groups neutralized with the metallic ions inanother embodiment, and from 20 to 60% in yet another embodiment, andfurther ranges as stated above. The polymer component i, derived fromethylene in one embodiment, can be linear or branched.

The ionomers or blends of two or more ionomers should be capable ofbeing formed into a sheet having a thickness of from 15 μm to 6 mm, andfrom 25 μm to 700 μm in another embodiment, and possess desiredproperties, i.e., a high or low gloss, scratch resistance, abrasionresistance, etc. Useful ionomers or ionomer blends have a peak melttemperature of greater than 75° C. in one embodiment, and between 75° C.and 100° C. in another embodiment, and between 75° C. and 95° C. in oneembodiment, and between 80° C. and 90° C. in another embodiment; and amelt index (MI) of between 0.1 dg/min and 30 dg/min (ASTM D1238,190/2.16) in one embodiment, from 0.2 to 8 dg/min in one embodiment,from 0.5 to 5 dg/min in another embodiment, and from 0.8 to 2.5 dg/minin yet another embodiment, wherein a desirable range may be anycombination of any upper MI limit with any lower MI limit describedherein.

The ionomers useful in the present invention should provide high scratchand impact resistance to the laminate and composite article. Theionomers or ionomer blends have a 1% secant flexural modulus (ASTMD-790) of greater than 50 MPa in one embodiment, and greater than 100MPa in another embodiment, and greater than 200 MPa in anotherembodiment, and greater than 400 MPa in yet another embodiment, between50 and 400 MPa in one embodiment, and from 100 to 350 MPa in anotherembodiment. Desirable ionomers are ethylene methacrylic acid copolymerionomers and ethylene acrylic acid copolymers ionomers and the like.Particularly desirable ionomers are those that are sodium or zinc saltsof acrylic acid or methacrylic acid copolymers.

Further, in a desirable embodiment, certain blends of ionomers based onethylene acrylic acid copolymer neutralized with divalent and monovalentmetal ions (cations) such as Zn²⁺ and Na⁺, display a synergistic MI“uplift” as disclosed in, for example, U.S. Pat. Nos. 5,210,138, and5,929,174 are useful. In one embodiment of the invention, one or more ofthe ionomer layers that make up the laminate is a blend of a firstionomer having an MI value of from 0.6 to 1.0 dg/min, and a secondionomer having an MI value of from 2.1 to 3.0 dg/min. The blend of thefirst and second ionomers includes from 45 wt % to 95 wt % of the firstionomer in one embodiment, and from 55 wt % to 85 wt % of the firstionomer in another embodiment, and from 65 wt % to 80 wt % of the firstionomer in yet another embodiment, and from 72 wt % to 78 wt % of thefirst ionomer in yet another embodiment, and 75 wt % of the firstionomer in yet another embodiment, wherein a desirable range may includeany upper wt % limit and any lower wt % limit described herein. Theblends may include blends of two or more ionomers having differentmetallation (different metals and/or different % of metallation),different MI values, or a combination of variables.

Other examples of ionomers useful in the present invention include, butare not limited to, butadiene-acrylic acid copolymer ionomers,perfluorsulfonate ionomers, perfluorocarboxylate ionomers, telechelicpolybutadiene ionomers, sulfonated ethylene-propylene-diene terpolymerionomers, styrene-acrylic acid copolymer ionomers, sulfonatedpolystyrene ionomers, sulfonated polypentenamer ionomers, telechelicpolyisobutylene sulfonated ionomers, alkyl methacrylate-sulfonatecopolymer ionomers, styrene-based polyampholytes ionomers and acid-amineionomers and the like. Typical examples of ionomers employing salts ofcarboxylic acid type pendent groups are disclosed in GB 1,011,981; U.S.Pat. Nos. 3,264,272; 3,322,734; 3,338,734; 3,355,319; 3,522,222; and3,522,223. Typical examples of ionomers employing phosphonate-typependent groups include those disclosed in U.S. Pat. Nos. 3,094,144;2,764,563, 3,097,194; and 3,255,130. Typical examples of ionomersemploying sulfonate-type pendent groups include those disclosed in U.S.Pat. Nos. 2,714,605; 3,072,618; and 3,205,285. Other useful ionomers aredisclosed generally in U.S. Pat. Nos. 5,631,328, 5,631,328, 5,554,698,4,801,649, 5,320,905, 5,973,046, and 4,569,865.

Ionomers comprising copolymers of ethylene derived units and acrylicacid (AA) derived units are desirable. Examples of commerciallyavailable ionomers include, but are not limited to, IOTEK ionomers(ExxonMobil Chemical Company, Houston, Tex.), such as IOTEK 8000, a 45%sodium neutralized ethylene-based ionomer of 15 wt % acrylic acid (priorto neutralization), and IOTEK 7030, a 25% zinc neutralizedethylene-based ionomer of 15 wt % acrylic acid, and SURLYN ionomers(DuPont Company, Wilmington, Del.).

The one or more ionomer layers may contain additives such asantioxidants, pigments or dyes, and other agents. In one embodiment, atleast one layer of ionomer in the final composite article will have apigment, antioxidant, or other additives. For external uses, it isdesirable to add a UV stabilizer such as TINUVEN 791 (CIBA SpecialtyChemicals) or UVASIL 2000 HM or LM (Great Lakes Chemicals), both siliconbased compositions. Also, for scratch resistance, it is advantageous toadd siloxane based compositions such as MB50-001 and/or MB50-321 (DowCorning Corporation). Effective levels are known in the art and dependon the details of the base polymers, the fabrication mode and therequirements of the end application. In addition, hydrogenated and/orpetroleum hydrocarbon resins and other plasticizers may be used asmodifiers.

Other examples of additives include one or more of the following: heatstabilizers or antioxidants, neutralizers, slip agents, antiblockagents, pigments, antifogging agents, antistatic agents, clarifiers,nucleating agents, ultraviolet absorbers or light stabilizers, fillers,rosins or rosin esters, waxes, additional plasticizers and otheradditives in conventional amounts. In one embodiment, a metallic ormetal flake pigment such as is used in the automotive industry may beused. The pigment may be included in a first, second, third ionomerlayer, or any other layer. For example, the pigment may desirably be ina second layer only, the first layer having no pigment and providinggloss and scratch resistance to the laminate. This second layer may havemetallic pigment or metal flake blend and be processed in a manner suchthat the final product has a shiny, metallic look, and changesappearance dependent upon the angle of view (“flop”) useful in, forexample, exterior automotive components, or a dull look useful in, forexample, interior automotive components.

Tie-Layer

In one embodiment, the tie-layer is made from a (co)extrudable tie resin(CTR). In another embodiment, the tie-layer may comprise one or morelayers of CTRs. In another embodiment, suitable CTRs include blends ofCTRs (as described below) and/or blends of at least one CTR withconventional materials known in the art, i.e., acid polymers, softionomers, and thermoplastics, etc. (See WO 02/078953 and WO 02/078954).

In some of the structural formulas below, some of the bonds are shownattached to only one atom instead of two. This indicates that the moietyshown is a small segment of the whole polymer and that the free ends ofthose bonds are actually attached to other components of the polymer.For simplicity, only the structure of the moiety being discussed in thetext is shown. One skilled in the art will understand this shorthandnotation, the types of “other components” to which the subject moietywould be attached for the particular polymer composition and the factthat the subject moiety might be present in many places in the polymer.

Suitable CTRs include amine-containing polymers. Amine-containingpolymers are copolymers of one or more C₂-C₁₀ α-olefins, preferablyethylene and/or propylene, and one or more ethylenically copolymerizableamine-containing monomer, the copolymer having amine groups that may berepresented by the general formula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon and R′ is abond or a C₁ to C₁₀ hydrocarbon.

In a preferred embodiment, R is H and R′ is a bond.

Other suitable CTRs include epoxy-containing copolymers and terpolymers.Epoxy-containing copolymers and terpolymers may be produced by directcopolymerization of C₂-C₁₀ α-olefins, preferably ethylene and/orpropylene, and epoxy-containing monomers such as glycidyl acrylate orglycidyl methacrylate, and for terpolymers, with other ester monomers.Epoxy-containing monomers may be represented by the general formula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon and R′ isindependently a bond or a C₁ to C₁₀ hydrocarbon. The polymers of thisinvention may be made using mixtures of monomers with different R and R′groups.

Alternatively, epoxy-containing polymers may be made with an estermonomer to form an epoxy-containing terpolymer. The ester monomer may berepresented by the general formula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon; each R′ isindependently a bond or a C₁ to C₁₀ hydrocarbon; and R″ is a C₁ to C₁₀hydrocarbon. The polymers of this invention may be made using mixturesof monomers with different R, R′ and R″ groups.

Preferred embodiments of epoxy-containing polymers include thecopolymers of ethylene and/or propylene with one or more ester monomersmethyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, orbutyl(meth)acrylate.

Epoxy-containing polymers may also be produced by graftingepoxy-containing monomers onto C₂-C₁₀ α-olefins polymers, preferablyethylene and/or propylene polymers and/or copolymers of C₂-C₁₀ α-olefinswith polar monomers such as vinyl esters and other ester monomers. Thesegrafted, epoxy-containing polymers may be represented by the generalformula:

In some embodiments, each polymer molecule can be grafted with anepoxy-containing monomer, such as glycidyl methacrylate, in severalplaces along the polymer chain.

Preferable embodiments include glycidyl methacrylate grafted ontopolyethylene or a copolymer of ethylene with one or more ester monomersmethyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, orbutyl(meth)acrylate.

Suitable CTRs also include acidic copolymers. Acidic copolymers includebipolymers of C₂-C₁₀ α-olefins, preferably ethylene and/or propylene,and acidic monomers that may be represented by the general formula:

where R is H or a C₁ to C₁₀ hydrocarbon and R′ is a bond or a C₁ to C₁₀hydrocarbon.

In some embodiments, the polymers of this invention may be made usingmixtures of acid monomers with different R and R′ substituents.Preferred embodiments are ethylene and/or propylene copolymerized withacrylic acid and/or methacrylic acid.

Suitable CTRs may also be bipolymers of C₂-C₁₀ α-olefins, preferablyethylene and/or propylene, and ethylenically copolymerizable estermonomers represented by the general formula:

where R is H or a C₁ to C₁₀ hydrocarbon; R′ is a bond or a C₁ to C₁₀hydrocarbon; and R″ is a C₁ to C₁₀ hydrocarbon.

The polymers of this invention may be made using mixtures of estermonomers with different R, R′ and R″ groups. Preferred embodiments areethylene and/or propylene copolymerized with one or more of estermonomers methyl(meth)acrylate, ethyl(meth)acrylate,propyl(meth)acrylate, or butyl(meth)acrylate.

Suitable CTRs include copolymers of C₂-C₁₀ α-olefins, preferablyethylene and/or propylene, and vinyl ester monomers represented by theformula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon.

Alternatively, vinyl ester copolymers may be made with other estermonomers to form terpolymers. The other ester monomer may be representedby the general formula:

where R is H or a C₁ to C₁₀ hydrocarbon; R′ is a bond or a C₁ to C₁₀hydrocarbon; and R″ is a C₁ to C₁₀ hydrocarbon.

The polymers of this invention may be made using mixtures of vinyl estermonomers and other ester monomers with different R, R′ and R″ groups.Preferred embodiments include ethylene or propylene copolymerized withvinyl acetate optionally with butyl(meth)acrylate.

Suitable CTRs also include grafted polymers of C₂-C₁₀ α-olefins,preferably ethylene and/or propylene, (such as LDPE, LLDPE, HDPE, PP, PPcopolymers, EPR or EPDM), ethylene vinyl ester copolymers (based on fromC₁ to C₁₀ acids), ethylene (meth)acrylate ester copolymers (made from C₁to C₁₀ alcohols) grafted with (meth)acrylic acid represented by thegeneral formula:

where each R is independently H or a C₁ to C₁₀ hydrocarbon and i is from1 to 5. Each polymer molecule can be grafted with methacrylic acid inseveral places along the polymer chain.

Suitable CTRs also include polymers made with unsaturated diacids,anhydrides of unsaturated diacids, or monoesters of unsaturated diacids.Suitable unsaturated diacids include, but are not limited to, maleicacid, itaconic acid, citraconic acid and 2-pentenedioic acid and theircorresponding anhydrides and monoesters. Illustrative examples may berepresented by the general formulas:

wherein for the monoester of maleic acid R is a C₁ to C₁₀ hydrocarbonand wherein for the monoesters of itaconic acid, citraconic acid and2-pentenedioic acid, either R′ is H and R″ is a C₁ to C₁₀ hydrocarbon orR′ is a C₁ to C₁₀ hydrocarbon and R″ is H.

Other suitable CTRs include copolymers of one or more C₂ to C₁₀α-olefins and carbon monoxide. These copolymers may be optionallycopolymerized with one or more ethylenically copolymerizable acidic orester monomers.

Ethylenically copolymerizable acidic monomers may be represented by thegeneral formula:

wherein R is H or a C₁ to C₁₀ hydrocarbon; R′ is a C₁ to C₁₀hydrocarbon; and n is 0 or 1. Preferred embodiments include acrylic acidand (meth)acrylic acid.

Ethylenically copolymerizable ester monomers of may be represented bythe following general formula:

wherein R is H or a C₁ to C₁₀ hydrocarbon; R′ is a C₁ to C₁₀hydrocarbon; R″ is a C₁ to C₁₀ hydrocarbon; and n is 0 or 1. Preferredembodiments include the group consisting of methyl(meth)acrylate,ethyl(meth)acrylate, propyl(meth)acrylate, and butyl(meth)acrylate.

Ethylenically copolymerizable vinyl ester monomers may be represented bythe following general formula:

wherein each R is independently H or a C₁ to C₁₀ hydrocarbon. Apreferred embodiment includes vinyl acetate.

In a preferred embodiment, the CTR is selected from the group consistingof an amine-containing polymer, an epoxy-containing polymer, a carbonmonoxide containing polymer, a polar copolymer, a polymer made from anunsaturated diacid, a polymer made from a monoester of an unsaturateddiacid, a polymer made from an anhydride of an unsaturated diacid, and apolyolefin grafted with acrylic acid.

In another preferred embodiment, the CTR is selected from the groupconsisting of an amine-containing polymer, an epoxy-containing polymer,a carbon monoxide containing polymer, an ester polymer, a vinyl esterpolymer, a polymer made from an unsaturated diacid, a polymer made froma monoester of an unsaturated diacid, a polymer made from an anhydrideof an unsaturated diacid, and a polyolefin grafted with acrylic acid.

CTRs useful in the invention have a melt index (MI ASTM D1238, 190/2.16)of from 0.1 to 60 dg/min in one embodiment, from 0.5 to 30 dg/min inanother embodiment, from 1 to 20 dg/min in yet another embodiment, andfrom 2.0 to 10 dg/min in yet another embodiment , a desirable rangeincluding a combination of any upper MI limit and any lower MI limitdisclosed herein.

In one embodiment, the backing layer is a blend of an appropriate CTR(selected independently from the CTR used in the tie-layer) and thematerial being used as the substrate material in the finished compositearticle. One skilled in the art will appreciate the need to selectmaterials based upon processing parameters, i.e. selecting low melt flowrates for extruding backing layers and higher melt flow rates forsubstrates that are injection molded and other parameters important forcreating a useful blend. General principles for making usefulpolymer-polymer blends can be found in the academic literature includingbooks such as Polymer Blends and Composite Articles, John A. Manson andLeslie H. Sperling, Plenum Press, New York, 1976, Polymer Blends, editedby D. R. Paul and Seymour Newman, Academic Press, New York, 1978,Specific Interactions and the Miscibility of Polymer Blends: PracticalGuides for Predicting & Designing Miscible Polymer Mixtures, Michael M.Coleman, John F. Graf, and Paul C. Painter, Technomic PublicationCompany, 1991, Polymeric Compatibilizers: Uses and Benefits in PolymerBlends, Sudhin Datta and David J. Lohse, Hanser/Gardner Publications,New York, 1996, Polymer Blends, edited by D. R. Paul and C. B. Bucknall,John Wiley & Sons, New York, 2000, and Polymer Blends Handbook, editedby L. A. Utracki, Kluwer Academic Press, Boston, 2003. The blend mayinclude from 10 wt % to 90 wt % of a CTR in the backing layer in oneembodiment, and from 20 wt % to 80 wt % in another embodiment, and from25 wt % to 65 wt % in yet another embodiment, and from 30 wt % to 50 wt% in yet another embodiment, based upon the total weight of the blend.In another embodiment, the blend comprises at least 10 wt % of a CTR,alternatively at least 15 wt %, alternatively at least 20 wt %, andalternatively at least 25 wt %, based upon the total weight of theblend. Desirable embodiments of the backing layer include anycombination of any upper CTR wt % limit and any lower CTR wt % limitdescribed herein.

The substrate materials used to blend with the at least one tie-layermaterial has a 1% secant flexural modulus (ASTM D-790) of greater than100 MPa in one embodiment, greater than 200 MPa in another embodiment,greater than 300 MPa in yet another embodiment, and greater than 500 MPain yet another embodiment, and greater than 900 MPa in yet anotherembodiment, and less than 1000 MPa in yet another embodiment.

The tie-layer may have a thickness in the range of from 2.5 μm to 6 mmin one embodiment, and from 25 μm to 650 μm in another embodiment, from2.5 μm to 400 μm in yet another embodiment, from 2 μm to 100 μm in yetanother embodiment, and from 10 μm to 1 mm in yet another embodiment.Desirable ranges may include any combination of any upper tie-layerthickness limit and any lower tie-layer thickness limit describedherein.

The tie-layer may also include additives as described above for theionomer layers, such as pigments, dyes, antioxidants, antiozonants, andother agents to improve its performance. Examples include one or more ofthe following: heat stabilizers or antioxidants, neutralizers, slipagents, antiblock agents, pigments, antifogging agents, antistaticagents, clarifiers, nucleating agents, ultraviolet absorbers or lightstabilizers, fillers, rosins or rosin esters, waxes, additionalplasticizers and other additives in conventional amounts.

Backing Layer

As stated above, a “backing layer” refers to a tie layer, on theopposite side of the surface ionomer layer of the multilayered laminate.In an embodiment that includes a substrate, the backing layer securesthe multilayer laminate to the substrate. In another embodiment, thebacking layer material comprises a blend of tie-layer material(s), asdescribed above, with substrate material(s) described below and/orsubstrate material(s) disclosed in WO 02/078953 A. However, in yetanother embodiment, the backing layer comprises at least one substratematerial described below.

When the backing layer comprises a blend, the blend may include from 10wt % to 90 wt % of tie-layer material(s) by weight of the backing layerblend in one embodiment, and from 20 wt % to 80 wt % in anotherembodiment, and from 25 wt % to 65 wt % in yet another embodiment, andfrom 40 wt % to 60 wt % in yet another embodiment, a desirableembodiment of the backing layer including any combination of any upperlimit and any lower limit of tie-layer materials described herein.

Substrate

A substrate material is a material, as described below, securable by anymeans known in the art, to the laminate. The substrate is contacted withand secured to the tie-layer to form a composite article. Substratematerials may be selected from the group comprisingacrylonitrile-ethylene-styrene (AES); acrylonitrile-styrene-acrylate(ASA); amorphous polyamides (made from mixed diacids, mixed diamines, orboth); isobutylene-based elastomers including butyl rubbers based onisobutylene with isoprene and other monomers, and copolymers ofisobutylene with alkylstyrene and other monomers, including thehalogenated versions of the aforementioned elastomers; chlorosulfonatedpolyethylene rubbers (Hypalon™ from DuPont, Wilmington, Del.);copolyester (PETG: cyclohexane dimethanol copolyester, and otherchemistries); cyclic olefin copolymer (COC); dynamically vulcanizedalloys (Santoprene™ and Geoplast™ from Advanced Elastomer Systems,Akron, Ohio, Keltalloy™ from Alliance Alloys, Leominster, Mass.,NexPrene™ from Harvest Polymers, Farnham, United Kingdom and similarproducts); liquid crystal polymers (LCP); natural rubber; generalpurposes rubbers; nitrile rubber; polyacrylonitrile (PAN); polyamidescompounds that are impact modified with acid and/or anhydride containingpolymers or rubbers; polyamide elastomers (Pebax™ from Atofina,Philadelphia, Pa., Vestamid™ from Degussa, Parsippany, N.J.);polyarylate (amorphous, aromatic polyester); polyaryletherketone (PAEK);polybenzimidazole; polybutylene terephthalate (PBT); polybutylenenaphthalate (PBN); polyester elastomers (such as Hytrel™ from DuPont,Riteflex™ from Ticona, Summit, N.J., Keyflex® BT from Harvest Polymers,Farnham, United Kingdom and similar products); polyethylene naphthalate(PEN); polyetherketone (PEK); polyethersulfone (PES); polyimidesulfone(PIS); polymethacrylate acrylonitrile butadiene styrene (MABS);polyphenylsulfone; polymethylmethacrylate (PMMA); polystyrene; highimpact polystyrene (HIPS); syndiotactic polystyrene; polystyrene maleicanhydride (SMA); polyethylene-vinyl alcohol (EVOH); sheet moldingcompounding (SMC) or a crosslinked, glass-reinforced,polyester/polystyrene composition; bulk molding compound (BMC);crosslinked polyurethane (RIM); reinforced polyurethane (RRIM),crosslinked dicyclopentadiene (Metton® RIM, Metton America, Inc,LaPorte, Tex.; silicone rubber; styrene block copolymers (SIS, SEBS);compression-molded articles of woven, glass-fiber-reinforcedpolypropylene fibers; or combinations thereof where appropriate.

In another embodiment, the substrate material may compriseacrylonitrile-ethylene-styrene (AES), acrylonitrile-styrene-acrylate(ASA), polymethacrylate acrylonitrile butadiene styrene (MABS),polyacrylonitrile (PAN), polymethylmethacrylate (PMMA),polyaryletherketone (PAEK), polybenzimidazole, polyetherketone (PEK),polyethersulfone (PES), polyimidesulfone (PIS), polyphenylsulfone(Radel™, Solvay), amorphous polyamides (made from mixed diacids, mixeddiamines, or both), polyamides compounds that are impact modified withacid and/or anhydride containing polymers or rubbers, polyamideelastomers (Pebax™ from Atofina, Philadelphia, Pa., Vestamid™ fromDegussa, Parsippany, N.J.), liquid crystal polymers (LCP), polyarylate(amorphous, aromatic polyester), polybutylene naphthalate (PBN),polybutylene terephthalate (PBT), polyethylene naphthalate (PEN),polyester elastomers (such as Hytrel™ from DuPont, Riteflex™ fromTicona, Summit, N.J., Keyflex® BT from Harvest Polymers, Farnham, UnitedKingdom and similar products), copolyester (PETG: cyclohexane dimethanolcopolyester, and other chemistries), crosslinked polyurethane (RIM),reinforced polyurethane (RRIM), natural rubber, general purposesrubbers, isobutylene-based elastomers including butyl rubbers based onisobutylene with isoprene and other monomers, and copolymers ofisobutylene with alkylstyrene and other monomers, including thehalogenated versions of the aforementioned elastomers, chlorosulfonatedpolyethylene rubbers (Hypalon™ from DuPont, Wilmington, Del.),dynamically vulcanized alloys (Santoprene™ and Geoplast™ from AdvancedElastomer Systems, Akron, Ohio, Keltalloy™ from Alliance Alloys,Leominster, Mass., NexPrene™ from Harvest Polymers, Farnham, UnitedKingdom and similar products), nitrile rubber, styrene block copolymers(SIS, SEBS), silicone rubber, polystyrene, syndiotactic polystyrene,high impact polystyrene (HIPS), polystyrene maleic anhydride (SMA), bulkmolding compound (BMC), sheet molding compounding (SMC) or acrosslinked, glass-reinforced, polyester/polystyrene composition, cyclicolefin copolymer (COC), crosslinked dicyclopentadiene (Metton® RIM,Metton America, Inc, LaPorte, Tex., polyethylene-vinyl alcohol (EVOH);or combinations thereof where appropriate.

The substrate materials described above may be used in foam form in someembodiments of the invention.

In one embodiment, the substrate materials may comprise mixtures of thesubstrate materials described above and/or mixtures with substratematerials disclosed in WO 02/067853 A1.

The substrate materials may also be combined with reinforcing and/ornon-reinforcing materials such as glass fibers, carbon fibers, carbonblack, polyaramide fibers, polyester fibers, mineral fibers, mica, talc,silica, metal whiskers, nanoclay, and the like. In a preferredembodiment, the fillers may be combined, for example in a blend, with asubstrate material by any suitable means known in the art to produce afilled blend.

Embodiments of the substrate material of the invention may containadditives. Additives may be included in the substrate formulations orany other ionomer layer or tie-layer disclosed herein, as suggested bythe intended uses of the materials and the knowledge and experience ofthe formulator. In one embodiment, included in any layer is a primaryantioxidant to deter oxidative degradation of the polymer and/or an acidscavenger to neutralized acid catalyst residues which may be present inthe polymer to a greater or lesser extent. Examples of the former classof additives would be hindered phenolic antioxidants and hindered aminelight stabilizers, examples and the application of which are welldocumented in the art. Examples of the latter category of additiveswould be metal salts of weak fatty acids such as sodium, calcium, orzinc stearate and weakly basic, naturally occurring minerals such ashydrotalcite or a synthetic equivalent like DHT-4A(Mg_(4.5)Al₂(OH)₁₃CO_(3.3.5)H₂O, Kyowa Chemical Industry Co., Ltd.,Kagawa, Japan).

Many other types of additives could be optionally included in the layerformulations of this invention such as flame retardants, lubricants,antistatic agents, slip agents, anti-blocking agents, colorants, metaldeactivators, mold release agents, fillers and reinforcements,fluorescent whitening agents, biostabilizers, and others.

Laminate Formation

The laminate may be formed by techniques well-known and practiced in theart. Illustrative examples of laminate formation processes includecoextrusion, thermal lamination, adhesive lamination, extrusionlamination and compression molding.

In one embodiment, the ionomer layer is adhered to the tie-layer in acoextrusion process. The coextrusion process can include 2, 3, 4 or morecoextruded layers. In general, the process includes first melting eachmaterial in an appropriate device and extruding these molten orsemi-molten materials together through a die or dies.

In one embodiment, extruders are used with a die that provides thermalisolation and/or control of each of the materials being processed toform the multilayer laminate. The temperature control can be achieved byany suitable means such as insulation and/or cooling and/or heatingelements that can be controlled by electricity, steam, oil, or othergases or liquids. Such a coextrusion apparatus is described in, forexample, U.S. Pat. Nos. 5,516,474 and 5,120,484, and references citedtherein. The extruder/die may have separate extrusion layers within thedie, and having a means by which to heat the material to a temperaturehigher than the melt temperature going into the die. For example, thedie may be controlled at a temperature from about 150° C. to 250° C.,while one or more of the material streams that will make up the laminatemay be further heated to from 230° C. to 300° C. Heating the layerhaving the pigment in this manner is particularly desirable. Thisprocedure improves the “flop” of the laminate, in particular whenmetallic pigments are used such as, for example, in an exteriorautomotive part.

Further, in some embodiments, the cooling of the laminate takes place ona chill roll or rolls, and may be cooled any number of ways. In oneembodiment, the cooling takes place at a chill roll temperature of from25° C. to 90° C. In yet another embodiment, the chill rolls are at from4° C. to 20° C. yielding a dull finish in the composite article whenusing a metallic pigment.

For more processing information, one skilled in the art will know toconsult the supplier or resources available from a technical library.The various layers can be combined in the melt stage via appropriatemechanisms known in the art prior to exiting the die, or combined afterexiting the die. This is followed by contacting the thus formedmulti-layered laminate with a series of chill rolls and sheet conveyer.The cooled laminate is then cut to size or rolled by appropriate means.Alternatively, one skilled in the art will appreciate that the variousmaterials can be extruded or calendered singly and combined into amultilayer structure in a separate process.

In one embodiment, the extrusion process conditions are as follows. Thetemperature controllers of the extruder(s) used to process theionomer(s) are set at 180° C. to 250° C. in one embodiment, yielding afinal material melt temperature of 200° C. to 225° C. or higher.Desirably, the ionomer material melt temperature is greater than 200° C.in another embodiment. The temperature controllers of the extruder(s)used to process the tie-layer(s) are set for 195° C. to 225° C. inanother embodiment, yielding a final material melt temperature of 210°C. to 230° C. The viscosity of each material being extruded should beclosely matched to each other, at their respective processingtemperatures, to achieve the targeted visual properties such as glosslevel and “flop” if needed, and interlayer bonding.

In one embodiment, the backing layer comprises an extrudable acrylicpolymer such as acrylonitrile-ethylene-styrene (AES),acrylonitrile-styrene-acrylate (ASA), polymethacrylate acrylonitrilebutadiene styrene (MABS), polymethylmethacrylate (PMMA). In order toavoid bubble formation during melt processing, these polymers may needto be dried prior to being extruded. Typical drying conditions are 2 to8 hours at 60° C. to 100° C. in a recirculating air dryer with someprovision for removing the moisture from the recirculating air. Themoisture can be removed from the recirculating air using desiccant bedsor mechanical refrigeration units or other appropriate means.Alternatively, vacuum dryers operating in similar temperature ranges canbe used. In one embodiment, for example, the acrylic polymer is extrudedat melt temperatures in the range of 150° C. to 200° C. In anotherembodiment, the melt temperature is between 240° C. and 280° C. Inanother embodiment, the melt temperature is between 180° C. and 225° C.

In another embodiment, the backing layer comprises an extrudableengineering thermoplastic polymer such as polyaryletherketone (PAEK),polybenzimidazole, polyetherketone (PEK), polyethersulfone (PES),polyimidesulfone (PIS), or polyphenylsulfone (Radel™, Solvay). In orderto avoid bubble formation during melt processing, these polymers willusually need to be dried prior to being extruded. Typical dryingconditions are 4 to 12 hours at 100° C. to 150° C. in a recirculatingair dryer with some provision for removing the moisture from therecirculating air. The moisture can be removed from the recirculatingair using desiccant beds or mechanical refrigeration units or otherappropriate means. Alternatively, vacuum dryers operating in similartemperature ranges can be used. In one embodiment, the engineeringthermoplastic polymer is extruded at melt temperatures in the range of200° C. to 400° C. In another embodiment, the melt temperature isbetween 250° C. and 325° C. In another embodiment, the melt temperatureis between 340° C. and 380° C. In another embodiment, the melttemperature is between 350° C. and 400° C. With these materials, it isuseful to keep the melt temperature from getting lower than targetbecause the viscosity will become too high causing problems incoextrusion, especially with layer thickness uniformity in thetransverse and also machine directions, and interlayer bonding will beadversely affected.

In yet another embodiment, the backing layer comprises an extrudablepolyamide such as amorphous polyamide (made from mixed diacids, mixeddiamines, or both), a polyamide compound that is impact modified withacid and/or anhydride containing polymers or rubbers, or polyamideelastomer (Pebax™ from Atofina, Philadelphia, Pa., Vestamid™ fromDegussa, Parsippany, N.J.). In order to avoid hydrolytic degradation andpossibly bubble formation during melt processing, these polymers willusually need to be dried prior to being extruded. Typical dryingconditions are 4 to 12 hours at 80° C. to 140° C. in a recirculating airdryer with some provision for removing the moisture from therecirculating air. The moisture can be removed from the recirculatingair using desiccant beds or mechanical refrigeration units or otherappropriate means. Alternatively, vacuum dryers operating in similartemperature ranges can be used. In one embodiment, the polyamide isextruded at melt temperatures in the range of 200° C. to 300° C. Inanother embodiment, the melt temperature is between 250° C. and 325° C.

In one embodiment, the backing layer comprises an extrudable polyesterssuch as liquid crystal polymers (LCP), polyarylate (amorphous, aromaticpolyester), polybutylene naphthalate (PBN), polybutylene terephthalate(PBT), polyethylene naphthalate (PEN), polyester elastomers (such asHytrel™ from DuPont, Riteflex™ from Ticona, Summit, N.J., Keyflex® BTfrom Harvest Polymers, Farnham, United Kingdom and similar products), orcopolyester (PETG: cyclohexane dimethanol copolyester, and otherchemistries). In order to avoid hydrolytic degradation and possiblybubble formation during melt processing, these polymers will usuallyneed to be dried prior to being extruded. Typical drying conditions are4 to 12 hours at 80° C. to 150° C. in a recirculating air dryer withsome provision for removing the moisture from the recirculating air. Themoisture can be removed from the recirculating air using desiccant bedsor mechanical refrigeration units or other appropriate means.Alternatively, vacuum dryers operating in similar temperature ranges canbe used. In one embodiment, the polyester is extruded at melttemperatures in the range of 190° C. to 400° C. In another embodiment,the melt temperature is between 330° C. and 400° C. In anotherembodiment, the melt temperature is between 260° C. and 300° C. Inanother embodiment, the melt temperature is between 250° C. and 290° C.In another embodiment, the melt temperature is between 190° C. and 240°C.

In another embodiment, the backing layer comprises an extrudablethermoplastic elastomer such as a dynamically vulcanized alloy or astyrene block copolymer. In one embodiment, the thermoplastic alloy isextruded at melt temperatures in the range of 150° C. to 250° C. Inanother embodiment, the melt temperature is between 200° C. and 250° C.In another embodiment, the melt temperature is between 180° C. and 225°C.

In yet another embodiment, the backing layer comprises an extrudablestyrenic polymer such as polystyrene, syndiotactic polystyrene, highimpact polystyrene (HIPS), or polystyrene maleic anhydride (SMA). In oneembodiment, the styrenic polymer is extruded at melt temperatures in therange of 150° C. to 300° C. In another embodiment, the melt temperatureis between 200° C. and 250° C. In another embodiment, the melttemperature is between 180° C. and 225° C.

In one embodiment, the backing layer comprises cyclic olefin copolymer(COC). In one embodiment, the cyclic olefin copolymer is extruded atmelt temperatures in the range of 150° C. to 300° C. In anotherembodiment, the melt temperature is between 200° C. and 250° C.

In another embodiment, the backing layer comprises polyethylene-vinylalcohol (EVOH). In one embodiment, the ethylene vinyl alcohol polymer isextruded at melt temperatures in the range of 150° C. to 250° C. Inanother embodiment, the melt temperature is between 200° C. and 250° C.In another embodiment, the melt temperature is between 180° C. and 225°C.

The aforementioned examples are provided for illustration and oneskilled in the art will appreciate the numerous variations possibleusing such methods and techniques well-known in the art. In no way arethey intended to limit the scope of the claimed invention unlessaffirmatively recited in the claims.

As recognized by an artisan, other laminate formation processes areuseful with the materials disclosed herein as all the materialsdescribed herein for the tie-layer, backing layer, and substrate do notreadily lend themselves to a (co)extrusion processes as described above.

Examples of such materials include polyacrylonitrile (PAN); crosslinkedpolyurethane (RIM); reinforced polyurethane (RRIM); natural rubber;general purposes rubbers; isobutylene-based elastomers including butylrubbers based on isobutylene with isoprene and other monomers; andcopolymers of isobutylene with alkylstyrene and other monomers;including the halogenated versions of the aforementioned elastomers;chlorosulfonated polyethylene rubbers (Hypalon™ from DuPont, Wilmington,Del.), dynamically vulcanized alloys (Santoprene™ and Geoplast™ fromAdvanced Elastomer Systems, Akron, Ohio, Keltalloy™ from AllianceAlloys, Leominster, Mass., NexPrene™ from Harvest Polymers, Farnham,United Kingdom and similar products); nitrile rubber; styrene blockcopolymers (SIS, SEBS); silicone rubber; bulk molding compound (BMC);sheet molding compounding (SMC) or a crosslinked, glass-reinforced,polyester/polystyrene composition; and crosslinked dicyclopentadiene(Metton® RIM, Metton America, Inc, LaPorte, Tex., as described in moredetail below.

In particular, in some embodiments, laminates are formed by adjoining amultilayer sheet of ionomer(s) and tie layer(s) to a backing layer bycompression molding the multilayer sheet with the backing layer. In oneembodiment, the backing layer, in substantially planar form, wasproduced in a separate process. This would be a particularly usefulprocess to make an ionomer-clad laminate with what is known in theindustry as “sheet molding compound” (crosslinkable, glass-reinforced,polyester/polystyrene composition in sheet form).

In another embodiment, the compression molding process is used toproduce an ionomer-clad laminate of the multilayer sheet adjoined tofiber reinforced polymers such as fiber reinforced polypropylene.

In another embodiment, this process is used to produce directly afinished article using a multilayer sheet adjoined to a substrate ofsheet molding compound by compression molding in matched-metal moldsthat have been machined to the shape of the desired finished article.

In some embodiments, laminates are formed by adjoining a multilayersheet of ionomer(s) and tie layer(s) to a backing layer by spraytechniques whereby the backing layer material is sprayed onto the tielayer side of the multilayer sheet of ionomer(s) and tie layer(s). Inone embodiment, the backing layer material is sprayed in a molten formonto the tie layer side of the multilayer sheet. In another embodiment,the backing layer, which has not been completely reacted, is sprayed inliquid form onto the tie layer side of the multilayer sheet and reactioncompleted in a subsequent process step. In another embodiment, thisprocess is used to produce directly a composite article comprising themultilayer sheet and the substrate material, which has not beencompletely reacted, sprayed onto the tie layer side of the multilayersheet and reaction completed in a subsequent process step. In anotherembodiment, this process is used to produce directly a finished articlecomprising the multilayer sheet and the substrate material, which hasnot been completely reacted, sprayed onto the tie layer side of themultilayer sheet and reaction completed in a subsequent shaping processstep.

In some embodiments, laminates are formed by adjoining a multilayersheet of ionomer(s) and tie layer(s) to a backing layer by adhesivebonding. This would be a particularly useful process to make anionomer-clad laminate comprising a multilayer sheet of ionomer(s) andtie layer(s) adhesively bonded to a sheet of cured rubber. The curedrubber sheet can be produced from natural rubber, general purposerubbers, isobutylene-based elastomers including butyl rubbers based onisobutylene with isoprene and other monomers, and copolymers ofisobutylene with alkylstyrene and other monomers, including thehalogenated versions of the aforementioned elastomers, chlorosulfonatedpolyethylene rubbers, nitrile rubbers, silicone rubbers or mixturesthereof.

In one embodiment, a laminate is formed by adjoining a multilayer sheetof ionomer(s) and tie layer(s) to a backing layer of crosslinkeddicyclopentadiene using a compression molding process. In thisembodiment, the backing layer of crosslinked dicyclopentadiene wasproduced in a separate process.

In one embodiment, a composite article is formed by adjoining amultilayer sheet of ionomer(s) and tie layer(s) to a substrate layer ofcrosslinked dicyclopentadiene using a compression molding process. Inthis embodiment, the substrate layer of crosslinked dicyclopentadienewas produced in a separate process.

In one embodiment, a finished article is formed by adjoining amultilayer sheet of ionomer(s) and tie layer(s) to a substrate layer ofcrosslinked dicyclopentadiene using an adhesive. In this embodiment, thesubstrate layer of crosslinked dicyclopentadiene was produced to thedesired shape of the finished article in a separate process.

In one embodiment, a finished article is formed by using an adhesive toadjoin a multilayer sheet of ionomer(s) and tie layer(s) to a substratethat is an article produced by the reactive injection molding of aurethane. In this embodiment, the article to which the multilayer sheetwas adjoined was produced in the desired shape separately by thereactive injection molding process. In another embodiment, the reactiveinjection molded article is reinforced with one or more reinforcingfillers such as glass, polyaramide, wollastonite or other mineralfillers and the like.

In one embodiment, a finished article is formed by using an adhesive toadjoin a multilayer sheet of ionomer(s) and tie layer(s) to a substratethat is an article produced from sheet molding compound or bulk moldingcompound. In this embodiment, the article to which the multilayer sheetwas adjoined was produced in the desired shape separately by a moldingprocess performed on the sheet molding compound or bulk moldingcompound.

The aforementioned examples are provided for illustration and oneskilled in the art will appreciate the numerous variations possibleusing such methods and techniques well-known in the art. In no way arethey intended to limit the scope of the claimed invention unlessaffirmatively recited in the claims.

Regardless of the method to form the laminate, the final laminate mayhave any number of layers of ionomer and/or tie-layer materials.Embodiments of the laminate include one ionomer layer and one tie-layer.Another embodiment includes two layers of ionomer and a tie-layer. Inyet another embodiment, the laminate includes two layers of ionomer andtwo tie-layers. In yet another embodiment of the laminate, there may betwo layers of ionomer and a blend of tie-layer and substrate materials.

The final laminate may have any number of layers of ionomer andtie-layer materials. In one embodiment, the laminate is two layers,three in another embodiment, and four layers in yet another embodiment.In one embodiment, the ionomer layer or layers, prior to thermoforming,are from 13 μm to 1 mm. In another embodiment, the pre-thermoformedionomer layer or layers is from 25 μm to 380 μm. In yet anotherembodiment, the pre-thermoformed ionomer layer is from 200 μm to 380 μm.The tie-layer can be of comparable thickness ranges, making the overallthickness of the laminate from 100 μm to 5 mm in one embodiment, or from250 μm to 3 mm in yet another embodiment.

Additionally, one skilled in the art will recognize that the viscosityof each material to be extruded in adjoining layers should be closelymatched to each other, at their respective processing temperatures, toachieve the targeted visual properties such as gloss level and “flop” ifneeded, and interlayer bonding. This condition is especially true whenthere are three or more layers in the laminate. In some embodiments withonly two layers, the viscosity of the higher viscosity, adjoining layeris within less than 100% greater than the viscosity of the lowerviscosity, adjoining layer. In other embodiments with only two layers,the viscosity of the higher viscosity, adjoining layer is within lessthan 50% greater than the viscosity of the lower viscosity, adjoininglayer. In other embodiments with only two layers, the viscosity of thehigher viscosity, adjoining layer is within less than 25% greater thanthe viscosity of the lower viscosity, adjoining layer. Ideally, theviscosities of the two layers are essentially identical at theirrespective process temperatures. In embodiments involving three or morelayers, the principles for two-layer systems are applied in sequence toeach pair of adjoining layers.

Laminate Shaping Process

A shaped laminate may be produced by any suitable means known in theart. Thermoforming, vacuum forming, and blow molding are desirableembodiments.

Thermoforming is a process of forming at least one pliable plastic sheetinto a desired shape. Methods of thermoforming are well known in theart. For example, see McDonald, Joseph N., Thermoforming, ENCYCLOPEDIAOF POLYMER SCIENCE AND ENGINEERING, VOL. 16, John Wiley & Sons, 807-832(New York 1989). In an embodiment of the present invention, the laminatethat is formed from the at least one ionomer layer and tie-layer arethermoformed into a desirable shape, typically resembling the end usearticle. For illustration, an embodiment of the thermoforming sequenceis described. First, a piece of the laminate, cut to the appropriatesize, is placed on a shuttle rack to hold it during heating. The shuttlerack indexes into the oven which pre-heats the film before forming. Oncethe piece of the laminate is heated, the shuttle rack indexes back tothe forming tool. The piece of the laminate is then vacuumed onto theforming tool to hold it in place and the forming tool is closed. Theforming tool can be either a “male” or “female” type tool. The toolstays closed to cool the shaped laminate and the tool is then opened.The shaped laminate is then removed from the tool.

In certain embodiments, blow molding is a suitable laminate formingmeans, which includes injection blow molding, extrusion blow molding,and stretch blow molding. Blow molding is described in more detail in,for example, CONCISE ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING90-92 (Jacqueline I. Kroschwitz, ed., John Wiley & Sons 1990). Oneskilled in the art will know the appropriate processing conditions touse for blow molding. See, for example, WO 02/078953.

Composite Article Formation

Formation of the composite article may be achieved by any suitable meansknown to those skilled in the art. Illustrative examples include blowmolding, adhesive bonding, transfer molding, cast molding, cold forming,matched-die molding, injection molding, spray techniques, orcombinations thereof. See, for example, WO 02/078953 A and WO 02/078954A.

In one embodiment, these materials are coextruded in a multilayer die,then passed over at least two chill rolls and a sheet conveyor. Thiscooled sheet is then cut to size and/or rolled. Sheets taken from thiscooled material can then be placed on a thermoforming rack andthermoformed to conform substantially to the shape of an injectionmolding tool, followed by cooling of the shaped laminate, and trimmingof the cooled shaped laminate to prepare it for use in forming theshaped composite article. This trimmed, shaped laminate is then placedinto the injection molding tool exposing at least one layer of thetie-layer, in particular, the backing layer, in order to allow thetie-layer to be secured to the substrate material to be injected. Hence,the substrate material in molten form is then injected into the tool,forming a cohesive unit with the shaped laminate. The part that resultsis a composite article having the desired shape and geometry of the enduse article.

In an embodiment of the injection molding process, wherein a substratematerial is injection molded into a tool into which the shaped laminatehas been placed, the melt temperature of the substrate material isbetween 230° C. and 255° C. in one embodiment, and between 235° C. and250° C. in another embodiment, the fill time from 2 to 10 seconds in oneembodiment, from 2 to 8 seconds in another embodiment, and a tooltemperature of from 25° C. to 65° C. in one embodiment, and from 27° C.and 60° C. in another embodiment. In a desirable embodiment, thesubstrate material is at a temperature that is hot enough to melt thetie-layer material or backing layer to achieve adhesion between thelayers. Some substrate materials may require substantially differentprocessing temperatures well known in the art.

For example, many of the substrate materials cited above can beinjection molded into finished articles with a composite laminate on thesurface that would be visible when used to make the intended device.These include acrylic polymers, such as acrylonitrile-ethylene-styrene(AES), acrylonitrile-styrene-acrylate (ASA), polymethacrylateacrylonitrile butadiene styrene (MABS), and polymethylmethacrylate(PMMA); engineering thermoplastics such as polyaryletherketone (PAEK),polybenzimidazole, polyetherketone (PEK), polyethersulfone (PES),polyimidesulfone (PIS), polyphenylsulfone (Radel™, Solvay); polyamidessuch as amorphous polyamides (made from mixed diacids, mixed diamines,or both), polyamides compounds that are impact modified with acid and/oranhydride containing polymers or rubbers, and polyamide elastomers(Pebax™ from Atofina, Philadelphia, Pa., Vestamid™ from Degussa,Parsippany, N.J.); polyesters such as liquid crystal polymers (LCP),polyarylate (amorphous, aromatic polyester), polybutylene naphthalate(PBN), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN),polyester elastomers (such as Hytrel™ from DuPont, Riteflex™ fromTicona, Summit, N.J., Keyflex® BT from Harvest Polymers, Farnham, UnitedKingdom and similar products), copolyester (PETG: cyclohexane dimethanolcopolyester, and other chemistries); some elastomers such as dynamicallyvulcanized alloys (Santoprene™ and Geoplast™ from Advanced ElastomerSystems, Akron, Ohio, Keltalloy™ from Alliance Alloys, Leominster,Mass., NexPrene™ from Harvest Polymers, Farnham, United Kingdom andsimilar products), and styrene block copolymers (SIS, SEBS); styrenicpolymers such as polystyrene, syndiotactic polystyrene, high impactpolystyrene (HIPS), and polystyrene maleic anhydride (SMA); and cyclicolefin copolymer (COC).

In one embodiment, acrylic polymers are injection molded against anappropriate tie layer or backing side of a multilayer laminate to form afinished article. The injection molding conditions for acrylic polymersare well known in the art; for example, melt temperatures are typicallyin the range of 240° C. to 280° C. and mold temperatures are typicallyin the range of 40° C. to 80° C. Families of acrylic polymers andcertain grades within those families that are designed to have higherheat resistance might require slightly higher melt and moldtemperatures. Conversely, families of acrylic polymers and certaingrades within those families that have less heat resistance might bereadily injection moldable at slightly lower melt temperatures and allowlower mold temperatures to be used.

In one embodiment, engineering thermoplastic polymers are injectionmolded against an appropriate tie layer or backing side of a multilayerlaminate to form a finished article. The injection molding conditionsfor engineering thermoplastics are well known in the art; for example,melt temperatures are typically in the range of 280° C. to 350° C. andmold temperatures are typically in the range of 100° C. to 150° C. Thesematerials generally need to be dried prior to injection molding toprevent visual and physical defects in the molded parts. Typical dryingconditions are 4 to 12 hours at 100° C. to 150° C. in a recirculatingair dryer with some provision for removing the moisture from therecirculating air. The moisture can be removed from the recirculatingair using desiccant beds or mechanical refrigeration units or otherappropriate means. Alternatively, vacuum dryers operating in similartemperature ranges can be used.

Families of engineering thermoplastic polymers and certain grades withinthose families, that are designed to have higher heat resistance, mightrequire slightly higher melt and mold temperatures. Conversely, familiesof engineering thermoplastic polymers and certain grades within thosefamilies, that have less heat resistance, in particular those that arealloys with polymers that can be injection molded at lower temperatures,might be readily injection moldable at slightly lower melt temperaturesand allow lower mold temperatures to be used.

The relatively high melt and mold temperatures required to injectionmold engineering thermoplastics often necessitates very specializedmolding machines and molds and the development of a lot of processingtechnology to fabricate finished articles. Mold temperatures on the sideof the mold against which the ionomer surface of the multilayer sheet isplaced will need to be operated at considerably lower temperatures thanthe other side of the mold to assure the ionomer layer(s) are solidifiedwhen the part is ejected. Because the multilayer sheet is a good thermalinsulator, the mold temperature on that part of the mold can be a lotlower than the side of the mold in contact with the engineeringthermoplastic with out resulting in solidification of the moltenengineering thermoplastic too early in the molding process. Themultilayer sheet will be heated by the high temperature, engineeringthermoplastic polymer melt as it flows into the mold. The increase intemperature of the multilayer sheet will cause it to soften and becomedeformable. Care must be exercised during the filling step of theinjection molding process to prevent the multilayer sheet from beingdislodged by the flow of the engineering thermoplastic polymer.

In one embodiment, polyamide polymers are injection molded against anappropriate tie layer or backing side of a multilayer laminate to form afinished article. The injection molding conditions for polyamides arewell known in the art; for example, melt temperatures are typically inthe range of 240° C. to 320° C. and mold temperatures are typically inthe range of 50° C. to over 100° C. These materials need to be driedprior to injection molding to prevent degradation of the polyamide andalso visual and physical defects in the molded parts. Typical dryingconditions are 4 to 12 hours at 80° C. to 140° C. in a recirculating airdryer with some provision for removing the moisture from therecirculating air. The moisture can be removed from the recirculatingair using desiccant beds or mechanical refrigeration units or otherappropriate means. Alternatively, vacuum dryers operating in similartemperature ranges can be used. Families of polyamide polymers andcertain grades within those families that are designed to have higherheat resistance might require slightly higher melt and moldtemperatures. Conversely, families of polyamide polymers and certaingrades within those families that have less heat resistance might bereadily injection moldable at slightly lower melt temperatures and allowlower mold temperatures to be used.

In one embodiment, polyester polymers are injection molded against anappropriate tie layer or backing side of a multilayer laminate to form afinished article. The injection molding conditions for polyesters arewell known in the art; for example, melt temperatures are typically inthe range of 240° C. to 320° C. and mold temperatures are typically inthe range of 50° C. to over 100° C. These materials generally need to bedried prior to injection molding to prevent degradation of the polyesterand also visual and physical defects in the molded parts. Typical dryingconditions are 4 to 12 hours at 80° C. to 150° C. in a recirculating airdryer with some provision for removing the moisture from therecirculating air. The moisture can be removed from the recirculatingair using desiccant beds or mechanical refrigeration units or otherappropriate means. Alternatively, vacuum dryers operating in similartemperature ranges can be used. Families of polyester polymers andcertain grades within those families that are designed to have higherheat resistance might require slightly higher melt and moldtemperatures. Conversely, families of polyester polymers and certaingrades within those families that have less heat resistance might bereadily injection moldable at slightly lower melt temperatures and allowlower mold temperatures to be used.

The relatively high melt and mold temperatures required to injectionmold some polyesters often necessitates very specialized moldingmachines and molds and the development of a lot of processing technologyto fabricate finished articles. Mold temperatures on the side of themold against which the ionomer surface of the multilayer sheet is placedwill need to be operated at considerably lower temperatures than theother side of the mold to assure the ionomer layer(s) are solidifiedwhen the part is ejected. Because the multilayer sheet is a good thermalinsulator, the mold temperature on that part of the mold can be a lotlower than the side of the mold in contact with the engineeringthermoplastic with out resulting in solidification of the moltenengineering thermoplastic too early in the molding process. Themultilayer sheet will be heated by the high temperature, polyesterpolymer melt as it flows into the mold. The increase in temperature ofthe multilayer sheet will cause it to soften and become deformable. Caremust be exercised during the filling step of the injection moldingprocess to prevent the multilayer sheet from being dislodged by the flowof the polyester polymer.

The aforementioned examples are provided for illustration and oneskilled in the art will appreciate the numerous variations possibleusing such methods and techniques well-known in the art. In no way arethey intended to limit the scope of the claimed invention unlessaffirmatively recited in the claims.

It will be understood by those skilled in the art that the stepsoutlined above may be varied, depending upon the desired result. Forexample, the coextruded sheet of layered ionomer and tie-layer may bedirectly thermoformed without cooling, thus skipping a cooling step.Other parameters may be varied as well in order to achieve a finishedcomposite article having desirable features.

In another embodiment, the invention is a composite article including atleast one layer of ionomer material, a tie-layer securable to asubstrate material, and a substrate material secured to the tie-layer,the tie layer comprising at least one backing layer secured to thesubstrate, and wherein the backing layer comprises a blend of atie-layer material and a substrate material. The at least one ionomerlayer may further include both a surface layer and a sub-surface layerthat is secured to the tie-layer. The surface ionomer layer is desirablyclear or non-pigmented and have a thickness of from 75 to 150 μm,alternatively at least 100 μm. The substrate material may have a 1%secant flexural modulus of greater than 100 MPa.

INDUSTRIAL APPLICATIONS

The laminates and composite articles of the present invention can beused in various applications. They may be used in interior and exteriorcomponents of appliances such as clothing or dish washer exteriors,refrigerator door exteriors, refrigerator door interiors, refrigeratorliners, refrigerator housings.

The laminates and composite articles of the present invention can alsobe applied in construction. Some examples include tubs and showers,liners for tubs and showers, counter tops, floor coatings, laminatedsurface counter tops, polymer/wood composites, prefabricated buildingmaterials, sidings, sinks and sink liners, synthetic marble panels,translucent glass replacements, vinyl tiles, wall covering, and woodreplacements for decks.

Additionally, the laminates and composite articles of the presentinvention have utility in electronics for CDs and DVDs as well as forhousing on TVs, VCRs, computers, and stereos.

The laminates and composite articles of the present invention may alsobe used in a variety of sporting equipment and parts. Illustrativeexamples include boats, hulls, boat hulls, marine boat hulls/canoeinteriors and exteriors, boat covers, boat sails, jet skis (housings),skis, snowboards, snowmobiles, sports helmets, stadium seats,surfboards, helmets, and tent materials.

In other applications, the present invention is applied to exterior orinterior automotive parts. Illustrative examples include vehicularparts, automotive parts, airbag doors, doors, automotive door panels(interior and exterior), body chassis, body panels, bumpers, deck lids,fenders, hoods, rocker panels, mirror housings, dashboards, instrumentpanels, fuel tanks, grills, hopper cars, interior trims, pillar trims,cup holders, personal containers, and wheel covers. Applications withinthis category also include other minor components of any 2, 3, 4 or morewheeled vehicles including farm tractors; lawn and garden tractors; lawnmowers; large trucks; bicycles; toy wagons; parts for All TerrainVehicles (ATVs); parts for motorcycles such as fuel tanks; scooters;seat covers; helmets, and trims. They may also be used as protective andanti-icing surfacing for airplanes, helicopters, rockets, and shuttles.

The inventive laminates and composite articles may be used in lawn,yard, and garden applications as well. Some examples are lawn/outdoorfurniture, pool liners and covers, outdoor ornaments, and bird houses.

The inventive laminates and composite articles may also be used in cablejacketing, children's toys, clothing/fabric (combined with non-wovens),Gamma-radiation resistant applications, GORETEX™, luggage, and otherapplications for coating plastics and metals where a dull or glossy anda scratch resistant surface is desirable such as plastic microwaveablecookware, plastic paper goods, reflective signage and other reflectivearticles on roads and clothing, and wheels on in-line skates.

The aforementioned industrial applications may be combined with any ofthe embodiments described in the SUMMARY as well as any embodiments asclaimed.

While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to many differentvariations not illustrated herein. For these reasons, then, referenceshould be made solely to the appended claims for purposes of determiningthe true scope of the present invention.

Terms that are or may be trademarked in some jurisdictions are used inthe description. These terms are written in all capital letters, and isunderstood to recognize such trademarks. For brevity, markings such as“™” or “®” have not been used.

All priority documents are herein fully incorporated by reference forall jurisdictions in which such incorporation is permitted. Further, alldocuments cited herein, including testing procedures, publications,patents, journal articles, etc., are herein fully incorporated byreference for all jurisdictions in which such incorporation is permittedand only to the extent such disclosures are consistent with thedescription as herein provided.

1. A laminate comprising: an ionomer layer; a tie layer comprising atleast one acid-containing polymer; and a backing layer comprising atleast one polyamide polymer, at least one polyamide compound, at leastone polyamide elastomer, or mixtures thereof; wherein the tie-layer isdisposed between the ionomer layer and the backing layer.
 2. Thelaminate of claim 1, wherein the at least one acid-containing polymer isa terpolymer.
 3. The laminate of claim 2, wherein the terpolymercomprises an ester or carbon monoxide.
 4. The laminate of claim 1,wherein the at least one acid-containing polymer is a grafted polymer.5. The laminate of claim 1, wherein the at least one polyamide compoundcomprises amorphous polyamides.
 6. The laminate of claim 1, wherein theat least one polyamide compound is impact modified with acid and/oranhydride containing polymer(s) and/or rubber(s).
 7. The laminate ofclaim 1, wherein the ionomer layer comprises a first ionomer layer and asecond ionomer layer.
 8. The laminate of claim 7, wherein one or both ofthe first ionomer layer and the second ionomer layer is pigmented,natural, or clear.
 9. The laminate of claim 1, wherein the ionomer layercomprises a zinc-neutralized ionomer, a sodium-neutralized ionomer, or amixture thereof.
 10. The laminate of claim 1, wherein the backing layeris multilayered.
 11. The laminate of claim 1, wherein the backing layeris a blend.
 12. A composite article comprising a substrate and thelaminate of claim
 1. 13. The composite article of claim 12, wherein thethickness of the composite article is from 200 μm to 6 mm.
 14. Avehicle, an appliance, an automotive part, or a boat hull comprising thecomposite article of claim
 12. 15. A method of forming a compositearticle comprising: (a) obtaining a laminate comprising an ionomerlayer; a tie layer comprising at least one acid-containing polymer; anda backing layer comprising at least one polyamide polymer, at least onepolyamide compound, at least one polyamide elastomer, or mixturesthereof; and (b) securing a substrate to the laminate.
 16. The method ofclaim 15, wherein the laminate is a shaped laminate.
 17. The method ofclaim 15, wherein the at least one acid-containing polymer is aterpolymer.
 18. The method of claim 17, wherein the terpolymer comprisesan ester or carbon monoxide.
 19. The method of claim 15, wherein the atleast one acid-containing polymer is a grafted polymer.
 20. The methodof claim 15, wherein the at least one polyamide compound comprisesamorphous polyamides.
 21. The method of claim 15, wherein the at leastone polyamide compound is impact modified with acid and/or anhydridecontaining polymer(s) and/or rubber(s).
 22. The method of claim 15,wherein the ionomer layer comprises a first ionomer layer and a secondionomer layer.
 23. The method of claim 22, wherein one or both of thefirst ionomer layer and the second ionomer layer is pigmented, natural,or clear.
 24. The method of claim 15, wherein the ionomer layercomprises a zinc-neutralized ionomer, a sodium-neutralized ionomer, or amixture thereof.
 25. The method of claim 15, wherein the backing layeris multilayered.
 26. The method of claim 15, wherein the backing layeris a blend.
 27. The method of claim 15, wherein the thickness of thecomposite article is from 200 μm to 6 mm.
 28. A vehicle, an appliance,an automotive part, or a boat hull comprising the composite articleproduced by the method of claim
 15. 29. A composite article comprising:an ionomer layer; a tie layer comprising at least one acid-containingpolymer; and a substrate comprising at least one polyamide polymer, atleast one polyamide compound, at least one polyamide elastomer, ormixtures thereof.
 30. The composite article of claim 29, wherein the atleast one acid-containing polymer is a terpolymer.
 31. The compositearticle of claim 30, wherein the terpolymer comprises an ester or carbonmonoxide.
 32. The composite article of claim 29, wherein the at leastone acid-containing polymer is a grafted polymer.
 33. The compositearticle of claim 29, wherein the at least one polyamide compoundcomprises amorphous polyamides.
 34. The composite article of claim 29,wherein the at least one polyamide compound is impact modified with acidand/or anhydride containing polymer(s) and/or rubber(s).
 35. Thecomposite article of claim 29, wherein the ionomer layer comprises afirst ionomer layer and a second ionomer layer.
 36. The compositearticle of claim 35, wherein one or both of the first ionomer layer andthe second ionomer layer is pigmented, natural, or clear.
 37. Thecomposite article of claim 29, wherein the ionomer layer comprises azinc-neutralized ionomer, a sodium-neutralized ionomer, or a mixturethereof.
 38. The composite article of claim 29, wherein the tie-layer isdisposed between the ionomer layer and the substrate.
 39. The compositearticle of claim 29, wherein the substrate is a blend.
 40. The compositearticle of claim 29, wherein the thickness of the composite article isfrom 200 μm to 6 mm.
 41. A vehicle, an appliance, an automotive part, ora boat hull comprising the composite article of claim 29.